Protonation of Dppbz- and Binap-Ligated Rhodathiaboranes Yielding Hydron, Hydride, and Hydrogen Exchange
Year: 2024
Type: article
Abstract: The reaction of the 11-vertex rhodathiaborane [8,8,8-(H)(PPh 3 ) 2 -3-(NC 5 H 5 )- nido -7,8-RhSB 9 H 10 ] ( 1 ) with 1,2-bis(diphenylphosphine)benzene (dppbz) and ( S )-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) affords [1,1-(η 2 -dppbz)-3-(NC 5 H 5 )- closo -1,2-RhSB 9 H 8 ] ( 2 ) and [1,1-(η 2 -binap)-3-(NC 5 H 5 )- closo -1,2-RhSB 9 H 8 ] ( 3 ). These 11-vertex closo -rhodathiaborane chelates result from PPh 3 ligand substitution at the rhodium center and a nido -to- closo structural cluster transformation driven by H 2 loss. Treating compounds 2 and 3 with triflic acid (TfOH) leads to the formation of cationic clusters 4 and 5 . The hydrons bind to the polyhedral clusters, acquiring hydride character and providing chemical nonrigidity that manifests through metal vertex-to-thiaborane pseudo -rotations and concomitant hydron tautomerisms. The resulting cations react with hydrogen to form mixtures of hydrons, hydrogen, and hydridorhodathiaboranes in equilibrium. The reaction products are the result of heterolytic cleavage of the H–H bond, with full participation of the clusters and the addition of hydrogen atoms to the cages. In these reactions, there is a conversion of electrons and hydrons into hydrogen, and hydrogen into hydride ligands, demonstrating that these boron-based metal compounds act as electron reservoirs, capable of promoting multielectron processes.
Source: Inorganic Chemistry
Language: English
Topic: Boron Compounds in Chemistry
Subfield: Radiology, Nuclear Medicine and Imaging
Field: Medicine
Domain: Health Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W4403215666